Photochemical Dual Radical Coupling of Carboxylates with Alkenes/Heteroarenes via Diradical Equivalents DOI
Guanjie Wang,

Jingxin Ding,

J. Wu

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

Carboxylate diradical intermediates, with α-carbon and carboxylic oxygen acting as reactive radical centers, represent a highly attractive long-sought species in reaction design synthesis. However, capturing these intermediates for coupling reactions poses formidable challenge due to their inherent instability spontaneous decarboxylation. Here, we addressed this by temporarily masking the carboxylate reactivity via photocleavable dynamic oxygen–iodine bond. This approach effectively prevents unwanted decarboxylation enables controlled utilization of forming new bonds. Carboxylates alkenes/heteroarenes, among most readily available raw materials, can now seamlessly couple pathways form γ-butyrolactones, which are common motifs found numerous natural products bioactive molecules. Ionic traditional carboxylates ruled out based on experimental studies density functional theory (DFT) calculations. strategy overcomes substrate limitations methods, significantly expanding range applicable alkenes/heteroarenes. Our method allows transforming alkenes modes diverse offers insights into developing di- multiradical equivalents unprecedented synthetic designs.

Язык: Английский

Photochemical Dual Radical Coupling of Carboxylates with Alkenes/Heteroarenes via Diradical Equivalents DOI
Guanjie Wang,

Jingxin Ding,

J. Wu

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

Carboxylate diradical intermediates, with α-carbon and carboxylic oxygen acting as reactive radical centers, represent a highly attractive long-sought species in reaction design synthesis. However, capturing these intermediates for coupling reactions poses formidable challenge due to their inherent instability spontaneous decarboxylation. Here, we addressed this by temporarily masking the carboxylate reactivity via photocleavable dynamic oxygen–iodine bond. This approach effectively prevents unwanted decarboxylation enables controlled utilization of forming new bonds. Carboxylates alkenes/heteroarenes, among most readily available raw materials, can now seamlessly couple pathways form γ-butyrolactones, which are common motifs found numerous natural products bioactive molecules. Ionic traditional carboxylates ruled out based on experimental studies density functional theory (DFT) calculations. strategy overcomes substrate limitations methods, significantly expanding range applicable alkenes/heteroarenes. Our method allows transforming alkenes modes diverse offers insights into developing di- multiradical equivalents unprecedented synthetic designs.

Язык: Английский

Процитировано

0